WO2017115632A1 - 粘着剤用組成物、粘着剤層および粘着シート - Google Patents
粘着剤用組成物、粘着剤層および粘着シート Download PDFInfo
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- WO2017115632A1 WO2017115632A1 PCT/JP2016/086564 JP2016086564W WO2017115632A1 WO 2017115632 A1 WO2017115632 A1 WO 2017115632A1 JP 2016086564 W JP2016086564 W JP 2016086564W WO 2017115632 A1 WO2017115632 A1 WO 2017115632A1
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- pressure
- sensitive adhesive
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- 0 CO***CNC(NC***O*)=N Chemical compound CO***CNC(NC***O*)=N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
Definitions
- the present invention relates to an adhesive composition, an adhesive layer and an adhesive sheet.
- Patent Document 1 discloses a pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer containing a polymer component containing a specific acrylic polymer and a rosin-based tackifying resin or a terpene-based tackifying resin.
- Patent Document 2 discloses a pressure-sensitive adhesive composition containing a specific (meth) acrylic acid ester polymer and a polyfunctional isocyanate compound.
- the weight average molecular weight of the polymers disclosed in the examples of Patent Document 2 is 70,000 to 250,000, and the durability under high temperature conditions is not sufficient.
- An object of the present invention is to provide a pressure-sensitive adhesive layer that exhibits excellent adhesive force even when adhered to a polyolefin-based low-polarity material such as polypropylene, and can form an adhesive layer having excellent durability under a high-temperature load environment.
- the object is to provide a pharmaceutical composition.
- the present inventors diligently studied to solve the above problems. As a result, the present inventors have found that the above problems can be solved by a pressure-sensitive adhesive composition containing a specific (meth) acrylic polymer, a specific amount of a polyfunctional isocyanate compound, and a specific tackifier, thereby completing the present invention. It was.
- the present invention includes, for example, the following [1] to [6].
- RAFT reversible addition-fragmentation chain transfer
- the (meth) acrylic polymer (A) is a polymer of a polymerizable double bond-containing monomer in which the amount of the monomer having at least one selected from a hydroxyl group and an amino group is 0.3% by mass or less.
- the composition for adhesives as described in [1] or [2].
- each R 1 is independently a divalent organic group
- (A) is independently derived from a polymer of a polymerizable double bond-containing monomer containing a carboxyl group-containing monomer. Is a valent group.
- a pressure-sensitive adhesive layer that exhibits a good adhesive force even when adhered to a polyolefin-based low-polarity material such as polypropylene and can form an adhesive layer having excellent durability under a high temperature load environment.
- a pharmaceutical composition can be provided.
- composition for pressure-sensitive adhesives the pressure-sensitive adhesive layer, and the pressure-sensitive adhesive sheet of the present invention will be described.
- polymer is used to include homopolymers and copolymers
- polymerization is used to include homopolymerization and copolymerization.
- Acrylic and methacrylic are also collectively referred to as “(meth) acrylic”.
- the pressure-sensitive adhesive composition of the present invention includes a specific (meth) acrylic polymer (A) containing a specific (meth) acrylic acid ester polymer molecule (a) (hereinafter also referred to as “polymer molecule (a)”). And an isocyanate compound (B) having two or more isocyanate groups in one molecule (hereinafter also referred to as “polyfunctional isocyanate compound (B)”) and a specific tackifier (C).
- the (meth) acrylic polymer (A) contains a polymer molecule (a).
- the polymer molecule (a) has a structure represented by the formula (a1), has a hydroxyl group at both ends of the molecule, and has a structural unit derived from a carboxyl group-containing monomer.
- the polymer molecule (a) has a structure represented by the formula (a1) (hereinafter also referred to as “trithiocarbonate structure”).
- the pressure-sensitive adhesive layer obtained from the pressure-sensitive adhesive composition of the present invention can maintain high constant load peelability even at high temperatures and is considered to be excellent in durability. .
- the polymer molecule (a) has a structural unit derived from a carboxyl group-containing monomer.
- a carboxyl group-containing monomer can be used as the polymerizable double bond-containing monomer.
- the reaction between the hydroxyl group of the polymer molecule (a) and the isocyanate group of the polyfunctional isocyanate compound (B) can be promoted.
- a pressure-sensitive adhesive layer having excellent durability can be formed.
- the pressure-sensitive adhesive layer formed from the pressure-sensitive adhesive composition containing the polymer molecule (a) is made of a SUS plate or an aluminum plate. Excellent durability when attached to.
- the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the polymer molecule (a) is preferably 300,000 to 600,000, more preferably 320,000 to 550,000. More preferably, it is 330,000 to 500,000.
- the molecular weight distribution (Mw / Mn) of the polymer molecule (a) is preferably 4.0 or less, more preferably 1.5 to 3.8, still more preferably 1.8 to 3.5.
- Mw and Mw / Mn can be measured, for example, by the method described in Examples.
- the polymer molecule (a) is a reversible addition-cleavage of a polymerizable double bond-containing monomer such as (meth) acrylic acid ester to the compound represented by the formula (A1) (hereinafter also referred to as “compound (A1)”).
- a polymer obtained by polymerization by a chain transfer (RAFT) polymerization method is preferred.
- each R 1 is independently a divalent organic group.
- Compound (A1) has a trithiocarbonate structure in the molecule and has hydroxyl groups at both ends of the molecule.
- Compound (A1) can be synthesized, for example, according to the method described in JP-A-2007-230947. By using the compound (A1) having the above structure, a telechelic structure can be formed without containing harmful organic metals.
- the repeating structural unit derived from the polymerizable double bond-containing monomer is bonded almost uniformly to both sides of the trithiocarbonate structure in the molecule, and the hydroxyl group is bonded to both ends of the molecule.
- a chain polymer can be obtained.
- Examples of the compound (A1) include a compound represented by the formula (A2) (hereinafter also referred to as “compound (A2)”) and a compound represented by the formula (A3) (hereinafter also referred to as “compound (A3)”). .).
- Compound (A2) has a trithiocarbonate structure in the molecule and has one hydroxyl group at each end of the molecule.
- Examples of the compound (A2) include RAFT-NT manufactured by Nippon Terpene Chemical Co., Ltd.
- each X is independently —COO—, —CONR 3 — or a direct bond
- each R 3 is independently an alkyl group, and the alkyl group preferably has 1 to 4 carbon atoms.
- R 2 is independently an alkylene group, and the alkylene group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms;
- Ar is each independently a phenylene group or naphthylene; Or a group formed by substituting at least one of the aromatic ring hydrogen contained in the phenylene group or naphthylene group with a substituent. Examples of the substituent include an alkyl group and an alkoxy group.
- a carbonyl group in —COO— and —CONR 3 — is bonded to Ar.
- Two X are preferably the same group, two R 2 are preferably the same group, two R 3 are preferably the same group, and two Ar are the same group It is preferable.
- Compound (A3) has a trithiocarbonate structure in the molecule, and two hydroxyl groups at both ends of the molecule.
- Examples of the compound (A3) include RAFT-DiOH manufactured by Nippon Terpene Chemical Co., Ltd.
- X and Ar have the same meanings as the same symbols in the formula (A2); each R 4 independently represents an alkylene group, each R 5 independently represents a direct bond or an alkylene group,
- the alkylene group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms.
- Two X are preferably the same group, two R 4 are preferably the same group, two R 5 are preferably the same group, and two Ar are the same group It is preferable.
- Specific examples of the compound (A1) are shown below.
- RAFT polymerization a polymerizable double bond-containing monomer is polymerized in the presence of the compound (A1).
- the amount of compound (A1) to be used is generally 0.05 to 20 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the total amount of polymerizable double bond-containing monomers. If the amount of the compound (A1) used is not less than the lower limit of the range, the reaction control is easy, and if it is not more than the upper limit of the range, it is easy to adjust the weight average molecular weight of the resulting polymer to the above range. It is.
- the compound represented by the formula (A1-1) reacts such that a polymerizable double bond-containing monomer is inserted between a sulfur atom in the compound (A1) and a methylene group adjacent to the sulfur atom.
- a polymer hereinafter also referred to as “polymer (A1-1)”
- specific examples include a polymer represented by formula (A2-1) or formula (A3-1) (hereinafter referred to as “polymer (A2-1)”).
- polymer (A3-1) are examples of polymer represented by formula (A2-1) or formula (hereinafter referred to as “polymer (A2-1)”.
- polymer (A3-1) are examples of polymer represented by formula (A2-1) or formula (hereinafter referred to as “polymer (A2-1)”.
- R 1 has the same meaning as the same symbol in formula (A1), and (A) is derived from a polymer of a polymerizable double bond-containing monomer containing a carboxyl group-containing monomer. It is a divalent group (polymer chain of a polymerizable double bond-containing monomer).
- X, R 2 and Ar have the same meanings as the same symbols in the formula (A2), and (A) represents the weight of the polymerizable double bond-containing monomer including the carboxyl group-containing monomer. It is a divalent group derived from a coalescence (polymer chain of a polymerizable double bond-containing monomer).
- X, R 4 , R 5 and Ar have the same meanings as the same symbols in the formula (A3), and (A) each independently contains a polymerizable double bond containing a carboxyl group-containing monomer. It is a divalent group derived from a monomer polymer (polymer chain of a polymerizable double bond-containing monomer).
- A (a divalent group derived from a polymer) may be either a homopolymer structure or a copolymer structure of a polymerizable double bond-containing monomer. Further, the copolymer structure may be either a random copolymer structure of a polymerizable double bond-containing monomer or a block copolymer structure.
- the number of repeating structural units derived from the polymerizable double bond-containing monomer is the number of the polymer molecule (a).
- Mw is a number within the above range.
- the block copolymer structure is obtained by, for example, adding a polymerizable double bond-containing monomer to the compound (A1) and performing the first RAFT polymerization, and adding an additional polymerizable double bond to the obtained polymer. It can be obtained by adding a monomer and performing the second RAFT polymerization.
- a polymer represented by formula (A1-2) specifically, a polymer represented by formula (A2-2) or formula (A3-2) (hereinafter referred to as “polymer (A1-2)”, “polymer (A2-2)” And “polymer (A3-2)”.
- R 1 has the same meaning as the same symbol in formula (A1), and (A 1 ) and (A 2 ) are each independently a polymerizable double bond-containing monomer containing a carboxyl group-containing monomer It is a divalent group (polymer chain of a polymerizable double bond-containing monomer) derived from the polymer.
- X, R 2 and Ar have the same meanings as the same symbols in the formula (A2), and (A 1 ) and (A 2 ) are each independently a polymerizable group containing a carboxyl group-containing monomer. It is a divalent group (polymer chain of a polymerizable double bond-containing monomer) derived from a polymer of a heavy bond-containing monomer.
- X, R 4 , R 5 and Ar have the same meanings as the same symbols in formula (A3), and (A 1 ) and (A 2 ) each independently contain a carboxyl group-containing monomer. It is a divalent group (polymer chain of a polymerizable double bond-containing monomer) derived from a polymer of a polymerizable double bond-containing monomer.
- the polymer molecule (a) is a polymer in which the polymer chain of the polymerizable double bond-containing monomer has a block copolymer structure, such as polymers (A1-2) to (A3-2),
- the resulting pressure-sensitive adhesive composition has a good balance of hydrophobicity-hydrophilicity, flexibility-rigidity, etc., depending on the purpose.
- the RAFT polymer having the above structure has a soft segment derived from the polymer chain of the polymerizable double bond-containing monomer. Therefore, since the isocyanate group of the polyfunctional isocyanate compound (B) tends to approach the terminal hydroxyl group of the RAFT polymer, the formation of urethane bonds is considered to proceed efficiently.
- the polymer molecule (a) can be used alone or in combination of two or more.
- the (meth) acrylic polymer (A) may further contain a polymer other than the polymer molecule (a) in addition to the polymer molecule (a).
- Examples of the polymer other than the polymer molecule (a) include a by-product of RAFT polymerization when the polymer molecule (a) is produced by RAFT polymerization.
- the content of the polymer molecule (a) in the (meth) acrylic polymer (A) is not particularly defined as long as the polymer molecule (a) is contained in the (meth) acrylic polymer (A).
- the (meth) acrylic polymer (A) is obtained by, for example, RAFT polymerization.
- the (meth) acrylic polymer (A) is preferably a RAFT polymer of a polymerizable double bond-containing monomer including a carboxyl group-containing monomer.
- the polymerizable double bond-containing monomer used to form the (meth) acrylic polymer (A) is the same as the polymerizable double bond-containing monomer used to form the polymer molecule (a). It is preferable. That is, the polymer molecule (a) and a polymer other than the polymer molecule (a) contained in the (meth) acrylic polymer (A) are formed from the same polymerizable double bond-containing monomer. It is preferably a coalescence.
- the Mw measured by GPC of the (meth) acrylic polymer (A) is 300,000 to 600,000, preferably 320,000 to 550,000, more preferably 330,000 to 500,000.
- Mw / Mn of the (meth) acrylic polymer (A) is 4.0 or less, preferably 1.5 to 3.8, more preferably 1.8 to 3.5.
- the (meth) acrylic polymer (A) having a Mw / Mn in the above range has a uniform molecular weight and a small number of low molecular weight substances, so that the resulting crosslinked product is excellent in heat resistance and peels off a pressure sensitive adhesive sheet from a low temperature to a high temperature condition. Contamination of the adherend due to the low molecular weight material at the time can be suppressed.
- Mw and Mw / Mn can be measured, for example, by the method described in Examples.
- the content of the (meth) acrylic polymer (A) in the pressure-sensitive adhesive composition is usually 10 to 95% by mass in 100% by mass of the pressure-sensitive adhesive composition.
- the (meth) acrylic polymer (A) containing the polymer molecule (a) can be obtained by, for example, RAFT polymerization of the polymerizable double bond-containing monomer.
- the polymerizable double bond-containing monomer at least a (meth) acrylic acid ester and a carboxyl group-containing monomer are used.
- functional group-containing (meth) acrylates such as carboxyl group-containing (meth) acrylate, hydroxyl group-containing (meth) acrylate, and amino group-containing (meth) acrylate are excluded from the (meth) acrylic acid ester.
- polymerizable double bond-containing monomer at least one selected from functional group-containing monomers other than carboxyl groups and copolymerizable monomers other than these can be used.
- (meth) acrylic acid ester Since the polymer molecule (a) has a structural unit derived from (meth) acrylic acid ester, (meth) acrylic acid ester is used as the polymerizable double bond-containing monomer.
- the (meth) acrylic acid ester include alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, alkoxypolyalkylene glycol mono (meth) acrylate, alicyclic group, and aromatic ring-containing (meth) acrylate.
- the number of carbon atoms of the alkyl group in the alkyl (meth) acrylate is preferably 1-20.
- the alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, iso-propyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl ( (Meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, Decyl (meth) acrylate, undeca (meth) acrylate, lauryl (meth) acrylate, o
- alkoxyalkyl (meth) acrylate examples include methoxymethyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 3-ethoxypropyl ( And (meth) acrylate, 4-methoxybutyl (meth) acrylate, and 4-ethoxybutyl (meth) acrylate.
- alkoxypolyalkylene glycol mono (meth) acrylate examples include methoxydiethylene glycol mono (meth) acrylate, methoxydipropylene glycol mono (meth) acrylate, ethoxytriethylene glycol mono (meth) acrylate, ethoxydiethylene glycol mono (meth) acrylate, And methoxytriethylene glycol mono (meth) acrylate.
- Examples of the alicyclic group or aromatic ring-containing (meth) acrylate include cyclohexyl (meth) acrylate, benzyl (meth) acrylate, and phenyl (meth) acrylate.
- the (meth) acrylic acid ester can be used alone or in combination of two or more.
- the amount of the (meth) acrylic acid ester used is usually 70% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more with respect to 100% by mass of the total polymerizable double bond-containing monomer.
- the polymerizable double bond-containing monomer that forms A 1 and A 2 respectively is It is preferable that each of them contains different types of monomers selected from (meth) acrylic acid esters.
- carboxyl group-containing monomer examples include ⁇ -carboxyethyl (meth) acrylate, 5-carboxypentyl (meth) acrylate, mono (meth) acryloyloxyethyl ester succinate, and ⁇ -carboxypolycaprolactone mono (meth) acrylate.
- Carboxyl group-containing (meth) acrylates such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, fumaric acid, and maleic acid.
- the carboxyl group-containing monomer can be used alone or in combination of two or more.
- the use amount of the carboxyl group-containing monomer is usually 0.5 to 15% by mass, preferably 1 to 12% by mass, more preferably 3 to 10% by mass with respect to 100% by mass of the total polymerizable double bond-containing monomer. is there.
- ⁇ Functional group-containing monomer other than carboxyl group examples include acid group-containing monomers other than carboxyl groups, hydroxyl group-containing monomers, amino group-containing monomers, amide group-containing monomers, nitrogen-based heterocyclic-containing monomers, and cyano group-containing monomers.
- Examples of the acid group other than the carboxyl group include an acid anhydride group, a phosphoric acid group, and a sulfuric acid group.
- acid group-containing monomers other than carboxyl groups include acid anhydride group-containing monomers such as phthalic anhydride and maleic anhydride; phosphate group-containing monomers such as (meth) acrylic monomers having a phosphate group in the side chain A sulfuric acid group-containing monomer such as a (meth) acrylic monomer having a sulfuric acid group in the side chain.
- hydroxyl group-containing monomer examples include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl ( Examples include hydroxyl group-containing (meth) acrylates such as (meth) acrylate.
- amino group-containing monomer examples include amino group-containing (meth) acrylates such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate.
- Examples of the amide group-containing monomer include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, and N-hexyl (meth) acrylamide.
- Examples of the nitrogen heterocycle-containing monomer include vinyl pyrrolidone, acryloyl morpholine, and vinyl caprolactam.
- Examples of the cyano group-containing monomer include cyano (meth) acrylate and (meth) acrylonitrile.
- the functional group-containing monomer can be used alone or in combination of two or more.
- a monomer containing a functional group other than a carboxyl group may be used, but a copolymer of a monomer containing a functional group such as a hydroxyl group or an amino group that is highly reactive with an isocyanate group
- isocyanate crosslinking due to isocyanate crosslinking, the sites other than both ends of the molecule are crosslinked, and the free ends are increased by a certain amount, so that the durability of the resulting pressure-sensitive adhesive layer may be lowered.
- the amount of the monomer having at least one selected from a hydroxyl group and an amino group is preferably 0.3% by mass or less with respect to 100% by mass of the total polymerizable double bond-containing monomer. More preferably, it is 0.1% by mass or less.
- the polymer molecule (a) preferably has no structural unit derived from a monomer containing a functional group having reactivity with an isocyanate group.
- Copolymerizable monomers examples include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, propyl styrene, butyl styrene, hexyl styrene, heptyl styrene, octyl styrene, and other alkyl styrenes, fluorostyrene, chlorostyrene, bromostyrene, dibromo.
- styrene monomers such as styrene, iodinated styrene, nitrostyrene, acetylstyrene, and methoxystyrene, and vinyl acetate.
- the copolymerizable monomer can be used alone or in combination of two or more.
- RAFT polymerization is preferably performed in the presence of a polymerization initiator.
- the polymerization initiator include ordinary organic polymerization initiators. Specific examples include peroxides such as benzoyl peroxide and lauroyl peroxide, and 2,2′-azobisisobutyronitrile. An azo compound is mentioned. Among these, an azo compound is preferable.
- azo compound examples include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2-cyclopropyl). Propionitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile) 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 2,2′-azobis (2-amidinopropane) dihydrochloride, 2,2′-azobis ( N, N′-dimethyleneisobutylamidine), 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide], 2,2′-azo (Isobutylamide) dihydrate, 4,4′-azobis (4-cyanopen
- the polymerization initiator can be used alone or in combination of two or more.
- the amount of the polymerization initiator used is usually 0.001 to 2 parts by mass, preferably 0.002 to 1 part by mass with respect to 100 parts by mass of the polymerizable double bond-containing monomer.
- the Mw of the (meth) acrylic polymer (A) can be adjusted within an appropriate range.
- the reaction temperature in the RAFT polymerization method is usually 60 to 120 ° C., preferably 70 to 110 ° C., and is usually performed in an inert gas atmosphere such as nitrogen gas.
- the reaction can be performed under any conditions, and is usually performed at normal pressure.
- the reaction time is usually 1 to 20 hours, preferably 2 to 14 hours.
- JP-A-2007-230947 and JP-A-2011-52057 can be referred to.
- reaction solvent examples include aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane and n-octane; cyclopentane, cyclohexane and cycloheptane.
- Cycloaliphatic hydrocarbons such as cyclooctane; ethers such as diethyl ether, diisopropyl ether, 1,2-dimethoxyethane, dibutyl ether, tetrahydrofuran, dioxane, anisole, phenylethyl ether, diphenyl ether; chloroform, carbon tetrachloride, Halogenated hydrocarbons such as 1,2-dichloroethane and chlorobenzene; esters such as ethyl acetate, propyl acetate, butyl acetate and methyl propionate; acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, cyclohexane Ketones such as non; amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; nitriles such as ace
- the polyfunctional isocyanate compound (B) is an isocyanate compound having two or more isocyanate groups in one molecule.
- the number of isocyanate groups in one molecule of the polyfunctional isocyanate compound (B) is preferably 2 to 8, more preferably 3 to 5.
- the number of isocyanate groups is within the above range, it is preferable from the viewpoint of the crosslinking reaction efficiency between the polymer molecule (a) and the isocyanate compound, and the availability.
- diisocyanate compound having 2 isocyanate groups in one molecule examples include aliphatic diisocyanate, alicyclic diisocyanate, and aromatic diisocyanate.
- Aliphatic diisocyanates include ethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2-methyl-1,5-pentane diisocyanate, 3-methyl-1,5-pentane diisocyanate, 2,2,4-trimethyl
- aliphatic diisocyanates having 4 to 30 carbon atoms such as -1,6-hexamethylene diisocyanate.
- alicyclic diisocyanates examples include alicyclic rings having 7 to 30 carbon atoms such as isophorone diisocyanate, cyclopentyl diisocyanate, cyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated tetramethylxylylene diisocyanate.
- Group diisocyanates examples include alicyclic rings having 7 to 30 carbon atoms such as isophorone diisocyanate, cyclopentyl diisocyanate, cyclohexyl diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, and hydrogenated tetramethylxylylene diisocyanate.
- aromatic diisocyanate examples include aromatic diisocyanates having 8 to 30 carbon atoms such as phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, naphthylene diisocyanate, diphenyl ether diisocyanate, diphenylmethane diisocyanate, and diphenylpropane diisocyanate.
- isocyanate compound having 3 or more isocyanate groups in one molecule examples include aromatic polyisocyanate, aliphatic polyisocyanate, and alicyclic polyisocyanate. Specific examples include 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, and 4,4 ', 4 "-triphenylmethane triisocyanate.
- Examples of the isocyanate compound include multimers (for example, dimers or trimers, biurets, and isocyanurates) and derivatives (for example, polyhydric alcohols) of the above isocyanate compounds having 2 or 3 isocyanate groups. Addition reaction product with two or more diisocyanate compounds) and polymer.
- Examples of the polyhydric alcohol in the derivative include trivalent or higher alcohols such as trimethylolpropane, glycerin and pentaerythritol as low molecular weight polyhydric alcohols; high molecular weight polyhydric alcohols such as polyether polyols, Examples include polyester polyol, acrylic polyol, polybutadiene polyol, and polyisoprene polyol.
- isocyanate compounds include diphenylmethane diisocyanate trimer, polymethylene polyphenyl polyisocyanate, hexamethylene diisocyanate or tolylene diisocyanate biuret or isocyanurate, trimethylolpropane and tolylene diisocyanate or xylylene diisocyanate.
- Reaction product for example, a trimolecular adduct of tolylene diisocyanate or xylylene diisocyanate
- reaction product of trimethylolpropane and hexamethylene diisocyanate for example, a trimolecular adduct of hexamethylene diisocyanate
- polyether polyisocyanate for example, a polyether polyisocyanate
- Polyester polyisocyanate is mentioned.
- the polyfunctional isocyanate compound (B) can be used alone or in combination of two or more.
- the content of the polyfunctional isocyanate compound (B) in the pressure-sensitive adhesive composition is 0.1 to 5 parts by mass, preferably 0.5 to 4 parts by mass, with respect to 100 parts by mass of the (meth) acrylic polymer (A). Part, more preferably 1 to 3 parts by weight.
- the content of the compound (B) is in the above range, the cohesiveness of the resulting composition does not decrease, and the pressure-sensitive adhesive layer is excellent in the balance of adhesive properties of the resulting composition and excellent in durability.
- composition for pressure-sensitive adhesives of the present invention contains a tackifier (C), it can form a pressure-sensitive adhesive layer that exhibits good adhesive force even when adhered to a polyolefin-based low polarity material such as polypropylene. .
- the softening point of the tackifier (C) is 95 ° C. or higher, more preferably 95 to 150 ° C. If the tackifier (C) has a softening point within the above range, the pressure-sensitive adhesive layer has an appropriate tackiness and is excellent in heat resistance, so that a pressure-sensitive adhesive layer excellent in durability in a high-temperature environment can be obtained. Therefore, it is preferable.
- the softening point can be measured, for example, by differential scanning calorimetry (DSC) from 23 ° C. to 180 ° C. at a heating rate of 5 ° C. per minute.
- tackifier (C) examples include rosin compounds such as rosin ester resins; terpene compounds such as terpene phenol resins.
- rosin ester resin examples include disproportionated rosin ester resin, hydrogenated rosin ester resin, and polymerized rosin ester resin.
- Examples of the disproportionated rosin ester resin include super ester A-100 (Arakawa Chemical Industries, softening point 95 to 105 ° C.) and super ester A-115 (Arakawa Chemical Industries, softening point 108 to 120 ° C.). ), Superester A-125 (Arakawa Chemical Industries, softening point 120-130 ° C.).
- Examples of the hydrogenated rosin ester resin include Pine Crystal KE-604 (Arakawa Chemical Industries, softening point 124-134 ° C.) and Pine Crystal KE-140 (Arakawa Chemical Industries, softening point 130-150 ° C.). Is mentioned.
- Examples of the polymerized rosin ester resin include Pencel A (Arakawa Chemical Industries, softening point 100 ° C. or higher), Pencel C (Arakawa Chemical Industries, softening point 117-127 ° C.), Pencel D-125 (Arakawa Chemical). Manufactured by Kogyo Co., Ltd., softening point 120-130 ° C), Pencel D-135 (Arakawa Chemical Industries, softening point 130-140 ° C), Pencel D-160 (Arakawa Chemical Industries, softening point 150-165 ° C) Can be mentioned.
- terpene phenol resin examples include YS Polystar G150 (manufactured by Yasuhara Chemical, softening point 145 to 155 ° C.), YS Polystar G125 (manufactured by Yashara Chemical, softening point 120 to 130 ° C.), YS Polystar T100 (manufactured by Yashara Chemical, softening).
- YS Polystar T115 (manufactured by Yashara Chemical Co., softening point 110-120 ° C), YS Polystar T130 (manufactured by Yashara Chemical Co., softening point 125-135 ° C), YS Polystar T145 (manufactured by Yashara Chemical Co., softening point 140) -150 ° C), Tamanol 80L (Arakawa Chemical Industries, softening point 145-160 ° C), Tamanoru 901 (Arakawa Chemical Industries, softening point 120-135 ° C).
- These tackifiers (C) may be used alone or in combination of two or more.
- the content of the tackifier (C) in the pressure-sensitive adhesive composition is usually 5 to 50 parts by mass, preferably 8 to 40 parts by mass, more preferably 100 parts by mass of the (meth) acrylic polymer (A). 10 to 30 parts by mass.
- the pressure-sensitive adhesive layer has an appropriate tackiness and is excellent in adhesive strength to olefinic low-polarity materials.
- the pressure-sensitive adhesive composition of the present invention is an organic solvent, an antistatic agent, an ultraviolet absorber, an antioxidant, and a tackifying resin other than the above (C) as long as the effects of the present invention are not impaired in addition to the above components.
- 1 type (s) or 2 or more types selected from a plasticizer, an antifoaming agent, a filler, a stabilizer, a softening agent, and a wettability adjusting agent may be contained.
- the reaction solvent described in the “polymerization conditions” column of RAFT polymerization can be used.
- a polymer solution containing a (meth) acrylic polymer (A) and a reaction solvent obtained by RAFT polymerization, a polyfunctional isocyanate compound (B) and a tackifier (C) are mixed to prepare a pressure-sensitive adhesive composition.
- the content of the organic solvent is usually 0 to 90% by mass, preferably 10 to 80% by mass.
- the pressure-sensitive adhesive layer of the present invention is a polyfunctional (meth) acrylic polymer (A) containing a (meth) acrylic acid ester polymer molecule (a) by crosslinking the above-mentioned pressure-sensitive adhesive composition. It can be obtained by crosslinking with an isocyanate compound (B).
- the pressure-sensitive adhesive layer thus obtained exhibits a good adhesive force even when adhered to a polyolefin-based low-polarity material such as polypropylene, and has excellent durability under a high-temperature load environment.
- the thickness of the pressure-sensitive adhesive layer is usually 3 to 100 ⁇ m, preferably 5 to 50 ⁇ m.
- the pressure-sensitive adhesive layer preferably has a gel fraction of 20 to 90% by mass, more preferably 30 to 80% by mass, from the viewpoint of suppressing distortion of the polarizing plate, improving cohesive force, adhesive force, and removability. Preferably, it is 40 to 70% by mass.
- the conditions for forming the pressure-sensitive adhesive layer are as follows.
- the composition is applied onto a support or a separator and dried at 60 to 120 ° C., preferably 70 to 110 ° C., usually for 1 to 5 minutes, preferably 2 to 4 minutes, to form a coating film.
- the pressure-sensitive adhesive layer is preferably formed under the following conditions. After applying the composition on a support or separator and applying the support or separator on the coating film formed under the above conditions, usually 3 days or more, preferably 7 to 10 days, usually 5 to 60 ° C., It is preferably cured in an environment of 15 to 40 ° C., usually 30 to 70% RH, preferably 40 to 70% RH. When crosslinking is performed under the aging conditions as described above, a crosslinked body (network polymer) can be efficiently formed.
- polyester films such as polyethylene terephthalate, plastic films such as polyethylene, polypropylene, and ethylene-vinyl acetate copolymer; non-woven fabrics; and paper separators.
- the pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer made of the above-described pressure-sensitive adhesive composition.
- This pressure-sensitive adhesive sheet preferably has a base material, and may have a separator on the pressure-sensitive adhesive layer.
- the pressure-sensitive adhesive sheet include a double-sided pressure-sensitive adhesive sheet having only the pressure-sensitive adhesive layer, a base material, and a double-sided pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer formed on both surfaces of the base material, the base material, and one of the base materials. Examples thereof include a single-sided pressure-sensitive adhesive sheet having the pressure-sensitive adhesive layer formed on the surface, and a pressure-sensitive adhesive sheet having a separator attached to a surface of the pressure-sensitive adhesive sheet that is not in contact with the base material.
- the film thickness of the pressure-sensitive adhesive layer is usually 3 to 100 ⁇ m, preferably 5 to 80 ⁇ m.
- the film thickness of the substrate and the separator is not particularly limited, but is usually 10 to 100 ⁇ m, preferably 25 to 50 ⁇ m.
- polyester films such as polyethylene terephthalate, plastic films such as polyethylene, polypropylene, and ethylene-vinyl acetate copolymer; non-woven fabrics; and paper separators.
- the pressure-sensitive adhesive sheet of the present invention exhibits good adhesive force even when adhered to polyolefin-based low-polarity materials such as polyethylene and polypropylene, and has excellent durability under a high temperature load environment.
- the pressure-sensitive adhesive sheet of the present invention can be widely used as an industrial pressure-sensitive adhesive sheet, but it can be used for a nonwoven fabric double-sided tape and a double-sided tape for laminating urethane foam, particularly used in automobile interiors and inside electronic devices. it can.
- Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) About the (meth) acrylic polymer, the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) by standard polystyrene conversion were calculated
- HLC-8120GPC manufactured by Tosoh Corporation
- -GPC column configuration The following five columns (all manufactured by Tosoh Corporation) (1) TSK-GEL HXL-H (guard column) (2) TSK-GEL G7000HXL (3) TSK-GEL GMHXL (4) TSK-GEL GMHXL (5) TSK-GEL G2500HXL Sample Concentration: As will be 1.0 mg / cm 3, diluting and mobile phase solvent with tetrahydrofuran: tetrahydrofuran Flow rate: 1.0 cm 3 / min -Column temperature: 40 ° C
- AIBN 2,2′-azobisisobutyronitrile
- a polymer solution containing the acrylic polymer (A1) was obtained.
- the molecular weight measured by GPC for the acrylic polymer (A1) contained in the obtained polymer solution was Mw: 380,000 and Mw / Mn: 2.4.
- the heating residue of the obtained polymer solution was 45% by mass.
- RAFT agent-1 bis [4- ⁇ ethyl- (2-hydroxyethyl) aminocarbonyl ⁇ -benzyl ]
- Trithiocarbonate RAFT agent-2 S, S-dibenzyltrithiocarbonate
- Example 1 A polymer solution containing the acrylic polymer (A1) obtained in Production Example A1 was mixed with D-125 (Arakawa Chemical Industries, softening point 120 to 130 ° C.) as a tackifier. To this mixture, L-45 (manufactured by Soken Chemical Co., Ltd., tolylene diisocyanate crosslinking agent, about 3 isocyanate groups in one molecule) was mixed as an isocyanate compound to obtain a pressure-sensitive adhesive composition. The blending amount of D-125 to 100 parts of acrylic polymer (A1) was 30 parts, and the blending amount of L-45 was 2.0 parts (both solid content ratio).
- the pressure-sensitive adhesive composition was applied on a paper separator (EKR-80D) that had been peeled off using a doctor blade after removing bubbles, so that the thickness after drying was 65 ⁇ m. The solvent was removed by drying for a minute.
- the obtained pressure-sensitive adhesive coating film was bonded to both sides of a 38 ⁇ m-thick nonwoven substrate and aged for 7 days in an environment of 23 ° C. and 65% RH.
- Paper separator / pressure-sensitive adhesive layer / non-woven fabric substrate / pressure-sensitive adhesive layer / A double-sided pressure-sensitive adhesive sheet comprising a paper separator and having a total tape thickness of 140 ⁇ m excluding the paper separators on both sides was obtained.
- Example 2 and 3 and Comparative Examples 1 to 6 In Example 1, the composition for adhesives and the double-sided adhesive sheet were obtained like Example 1 except having changed the composition component as described in Table 1.
- the tackifiers listed in Table 1 are as shown below.
- D-125 Rosin tack fire (Arakawa Chemical Co., Ltd., trade name: Pencel D-125, softening point: 120 to 130 ° C.)
- T145 Terpene phenol resin (manufactured by Yasuhara Chemical Co., Ltd., trade name: YS Polystar T145, softening point: 140 to 150 ° C.)
- A-75 Rosin tackifier (Arakawa Chemical Co., Ltd., trade name: Superester A-75, softening point: 70-80 ° C)
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- Adhesive Tapes (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
一般に、ポリエチレン、ポリプロピレンなどのポリオレフィン系低極性素材に、アクリル系ポリマーを主成分とする粘着剤を貼着する場合、良好な粘着力を発現させるためには、粘着剤中に適当なタッキファイヤーを添加する必要がある。
特許文献2には、特定の(メタ)アクリル酸エステル重合体と、多官能イソシアネート化合物とを含有する粘着剤用組成物が開示されている。しかしながら、特許文献2の実施例に開示される重合体の重量平均分子量は、70,000~250,000であり、高温条件下における耐久性が充分ではない。
[1] 式(a1)で表される構造を有し、分子の両末端に水酸基を有し、かつカルボキシル基含有モノマーに由来する構造単位を有する(メタ)アクリル酸エステル重合体分子(a)を含み、ゲルパーミエーションクロマトグラフィー法により測定される重量平均分子量(Mw)が300,000~600,000、分子量分布(Mw/Mn)が4.0以下である(メタ)アクリルポリマー(A)と、1分子中のイソシアネート基数が2以上であるイソシアネート化合物(B)を、前記(メタ)アクリルポリマー(A)100質量部に対して0.1~5質量部と、軟化点95℃以上のタッキファイヤー(C)とを含有する粘着剤用組成物。
なお、本明細書において、「重合体」とは単独重合体および共重合体を包含する意味で用い、また、「重合」とは単独重合および共重合を包含する意味で用いる。
また、アクリルおよびメタクリルを総称して「(メタ)アクリル」とも記載する。
本発明の粘着剤用組成物は、特定の(メタ)アクリル酸エステル重合体分子(a)(以下「重合体分子(a)」ともいう。)を含む特定の(メタ)アクリルポリマー(A)と、1分子中のイソシアネート基数が2以上であるイソシアネート化合物(B)(以下「多官能イソシアネート化合物(B)」ともいう。)と、特定のタッキファイヤー(C)とを含有する。
(メタ)アクリルポリマー(A)は、重合体分子(a)を含む。
〈(メタ)アクリル酸エステル重合体分子(a)〉
重合体分子(a)は、式(a1)で表される構造を有し、分子の両末端に水酸基を有し、かつカルボキシル基含有モノマーに由来する構造単位を有する。
MwおよびMw/Mnは、例えば、実施例に記載の方法で測定することができる。
化合物(A1)の具体例を以下に示す。
(メタ)アクリルポリマー(A)は、重合体分子(a)に加え、重合体分子(a)以外の重合体をさらに含んでもよい。重合体分子(a)以外の重合体としては、例えば、RAFT重合で重合体分子(a)を製造する場合、RAFT重合の副生成物が挙げられる。
(メタ)アクリルポリマー(A)は、例えば、RAFT重合により得られる。
(メタ)アクリルポリマー(A)を形成するために使用する重合性二重結合含有モノマーは、前記重合体分子(a)を形成するために使用する重合性二重結合含有モノマーと、同一であることが好ましい。つまり、前記重合体分子(a)と、(メタ)アクリルポリマー(A)に含まれる前記重合体分子(a)以外の重合体とが、同一の重合性二重結合含有モノマーから形成された重合体であることが好ましい。
粘着剤用組成物中の(メタ)アクリルポリマー(A)の含有量は、粘着剤用組成物100質量%中、通常10~95質量%である。
重合性二重結合含有モノマーを、例えば、RAFT重合することにより、重合体分子(a)を含む(メタ)アクリルポリマー(A)を得ることができる。重合性二重結合含有モノマーとして、少なくとも(メタ)アクリル酸エステルおよびカルボキシル基含有モノマーが用いられる。ただし、前記(メタ)アクリル酸エステルからは、カルボキシル基含有(メタ)アクリレート、水酸基含有(メタ)アクリレート、アミノ基含有(メタ)アクリレート等の官能基含有(メタ)アクリレートを除く。
重合体分子(a)が、(メタ)アクリル酸エステル由来の構造単位を有するために、重合性二重結合含有モノマーとして、(メタ)アクリル酸エステルが用いられる。
(メタ)アクリル酸エステルとしては、例えば、アルキル(メタ)アクリレート、アルコキシアルキル(メタ)アクリレート、アルコキシポリアルキレングリコールモノ(メタ)アクリレート、脂環式基または芳香環含有(メタ)アクリレートが挙げられる。
(メタ)アクリル酸エステルの使用量は、全重合性二重結合含有モノマー100質量%に対して、通常70質量%以上、好ましくは80質量%以上、より好ましくは90質量%以上である。
重合体分子(a)が、カルボキシル基含有モノマー由来の構造単位を有するために、重合性二重結合含有モノマーとして、カルボキシル基含有モノマーが用いられる。
カルボキシル基含有モノマーの使用量は、全重合性二重結合含有モノマー100質量%に対して、通常0.5~15質量%、好ましくは1~12質量%、より好ましくは3~10質量%である。
カルボキシル基以外の官能基含有モノマーとしては、例えば、カルボキシル基以外の酸基含有モノマー、水酸基含有モノマー、アミノ基含有モノマー、アミド基含有モノマー、窒素系複素環含有モノマー、シアノ基含有モノマーが挙げられる。カルボキシル基以外の酸基としては、例えば、酸無水物基、リン酸基、硫酸基が挙げられる。
重合体分子(a)の合成において、カルボキシル基以外の官能基含有モノマーを使用してもよいが、イソシアネート基との反応性が高い水酸基、アミノ基などの官能基を含有するモノマーの共重合体の場合、イソシアネート架橋により、分子の両末端以外の場所が架橋し、自由末端が一定量増加することで、結果として得られた粘着剤層の耐久性が低下することがある。よって耐久性向上の観点からは、水酸基およびアミノ基から選ばれる少なくとも1種を有するモノマーの使用量は、全重合性二重結合含有モノマー100質量%に対して、好ましくは0.3質量%以下、より好ましくは0.1質量%以下である。
重合体分子(a)は、イソシアネート基への反応性を持つ官能基を含有するモノマーに由来する構成単位を有しないことが好ましい。
共重合性モノマーとしては、例えば、スチレン、メチルスチレン、ジメチルスチレン、トリメチルスチレン、プロピルスチレン、ブチルスチレン、へキシルスチレン、ヘプチルスチレンおよびオクチルスチレン等のアルキルスチレン、フロロスチレン、クロロスチレン、ブロモスチレン、ジブロモスチレン、ヨウ化スチレン、ニトロスチレン、アセチルスチレンおよびメトキシスチレン等のスチレン系単量体、酢酸ビニルが挙げられる。
共重合性モノマーは1種単独で、または2種以上を使用することができる。
RAFT重合は、重合開始剤の存在下に行うことが好ましい。重合開始剤としては、例えば、通常の有機系重合開始剤が挙げられ、具体的には、過酸化ベンゾイル、過酸化ラウロイル等の過酸化物、2,2'-アゾビスイソブチロニトリル等のアゾ化合物が挙げられる。これらの中でも、アゾ化合物が好ましい。
重合開始剤の使用量は、重合性二重結合含有モノマー100質量部に対して、通常0.001~2質量部、好ましくは0.002~1質量部である。重合開始剤を前記範囲内で使用することにより、(メタ)アクリルポリマー(A)のMwを適切な範囲内に調整することができる。
RAFT重合法での反応温度は、通常60~120℃、好ましくは70~110℃であり、通常は窒素ガス等の不活性ガス雰囲気下で行われる、この反応は常圧、加圧および減圧のいずれの条件で行うこともでき、通常は常圧で行われる。また、反応時間は通常1~20時間、好ましくは2~14時間である。重合条件については、例えば、特開2007-230947号公報および特開2011-52057号公報を参照することができる。
多官能イソシアネート化合物(B)は、1分子中のイソシアネート基数が2以上のイソシアネート化合物である。多官能イソシアネート化合物(B)の、1分子中のイソシアネート基数は、好ましくは2~8、より好ましくは3~5である。イソシアネート基数が前記範囲にあると、重合体分子(a)とイソシアネート化合物との架橋反応効率の点、および入手容易性の観点で好ましい。
粘着剤用組成物中の多官能イソシアネート化合物(B)の含有量は、(メタ)アクリルポリマー(A)100質量部に対して、0.1~5質量部、好ましくは0.5~4質量部、より好ましくは1~3質量部である。化合物(B)の含有量が前記範囲にあると、得られる組成物の凝集性が低下することがなく、また得られる組成物の粘着物性のバランスに優れ、耐久性に優れた粘着剤層を得ることができる。特に化合物(B)を前記下限値以上で使用すると、末端水酸基とイソシアネート基との反応率が向上し、充分に硬化するため粘着性能を発現することができるため好ましい。
本発明の粘着剤用組成物は、タッキファイヤー(C)を含有するため、ポリプロピレンなどのポリオレフィン系低極性素材への貼着においても良好な粘着力を発揮する粘着剤層を形成することができる。
前記ロジンエステル樹脂としては、例えば、不均化ロジンエステル樹脂、水添ロジンエステル樹脂、重合ロジンエステル樹脂が挙げられる。
これらのタッキファイヤー(C)は、単独で用いてもよく、2種以上を併用してもよい。
本発明の粘着剤用組成物は、上記成分のほか、さらに本発明の効果を損なわない範囲で、有機溶媒、帯電防止剤、紫外線吸収剤、酸化防止剤、前記(C)以外の粘着付与樹脂、可塑剤、消泡剤、充填剤、安定剤、軟化剤、および濡れ性調整剤から選択される1種または2種以上を含有してもよい。
本発明の粘着剤層は、上述の粘着剤用組成物を架橋することにより、具体的には(メタ)アクリル酸エステル重合体分子(a)を含む(メタ)アクリルポリマー(A)を多官能イソシアネート化合物(B)で架橋することにより得ることができる。このようにして得られる粘着剤層は、ポリプロピレンなどのポリオレフィン系低極性素材への貼着においても良好な粘着力を発揮し、かつ高温荷重環境下での秀逸な耐久性を有する。
粘着剤層は、偏光板の歪みの抑制、凝集力、接着力、再剥離性の向上の観点から、ゲル分率が、好ましくは20~90質量%、より好ましくは30~80質量%、さらに好ましくは40~70質量%である。
本発明の粘着シートは、上述の粘着剤用組成物からなる粘着剤層を有する。この粘着シートは、基材を有することが好ましく、粘着剤層上にセパレーターを有していてもよい。粘着シートとしては、例えば、上記粘着剤層のみを有する両面粘着シート、基材と、基材の両面に形成された上記粘着剤層とを有する両面粘着シート、基材と、基材の一方の面に形成された上記粘着剤層を有する片面粘着シート、およびそれら粘着シートの粘着剤層の基材と接していない面にセパレーターが貼付された粘着シートが挙げられる。
実施例における各測定値は、以下の方法により求めた。
(メタ)アクリルポリマーについて、ゲルパーミエーションクロマトグラフィー(GPC)法により、下記条件で標準ポリスチレン換算による重量平均分子量(Mw)および分子量分布(Mw/Mn)を求めた。
・測定装置:HLC-8120GPC(東ソー(株)製)
・GPCカラム構成:以下の5連カラム(すべて東ソー(株)製)
(1)TSK-GEL HXL-H (ガードカラム)
(2)TSK-GEL G7000HXL
(3)TSK-GEL GMHXL
(4)TSK-GEL GMHXL
(5)TSK-GEL G2500HXL
・サンプル濃度:1.0mg/cm3となるように、テトラヒドロフランで希釈
・移動相溶媒:テトラヒドロフラン
・流量:1.0cm3/min
・カラム温度:40℃
精秤したブリキシャーレ(質量:n1)に(メタ)アクリルポリマー溶液1gを入れ、合計質量(n2)を精秤した後、105℃で3時間加熱した。その後、当該ブリキシャーレを室温のデシケータ内に1時間静置し、次いで再度精秤し、加熱後の合計質量(n3)を測定した。得られた質量測定値(n1~n3)を用いて、下記式から加熱残分を算出した。
加熱残分(質量%)=100×[加熱後質量(n3-n1)/加熱前質量(n2-n1)]
[製造例A1]
攪拌装置、窒素ガス導入管、温度計および還流冷却管を備えたフラスコに、n-ブチルアクリレート44部、2-エチルヘキシルアクリレート50部、アクリル酸6部、およびビス[4-{エチル-(2-ヒドロキシエチル)アミノカルボニル}-ベンジル]トリチオカーボネート(日本テルペン化学(株)製)(以下「RAFT剤-1」ともいう。)0.1部を仕込み、フラスコ内に窒素ガスを導入しながらフラスコの内容物を80℃に加熱した。
製造例A1において、成分組成を表1に記載したとおりに変更したこと以外は製造例1と同様にして、アクリルポリマー(A2)および(B1)~(B4)を含むポリマー溶液を得た。なお、製造例B1では、酢酸エチルは、フラスコ内の内容物の温度を80℃に保ったまま1時間かけて60部滴下し、最後に20部添加した。
表1に記載の各成分は以下に示すとおりである。
BA:n-ブチルアクリレート
2-EHA:2-エチルヘキシルアクリレート
2-HEA:2-ヒドロキシエチルアクリレート
AA:アクリル酸
RAFT剤-1:ビス[4-{エチル-(2-ヒドロキシエチル)アミノカルボニル}-ベンジル]トリチオカーボネート
RAFT剤-2:S,S-ジベンジルトリチオカーボネート
[実施例1]
製造例A1で得られたアクリルポリマー(A1)を含むポリマー溶液と、タッキファイヤーとしてD-125(荒川化学工業社製、軟化点120~130℃)とを混合した。この混合物に、イソシアネート化合物としてL-45(綜研化学(株)製,トリレンジイソシアネート系架橋剤、1分子中のイソシアネート基数約3)を混合し粘着剤用組成物を得た。なお、アクリルポリマー(A1)100部に対するD-125の配合量が30部、L-45の配合量が2.0部となる割合(いずれも固形分比)で混合した。
実施例1において、組成成分を表1に記載したとおりに変更したこと以外は実施例1と同様にして、粘着剤用組成物および両面粘着シートを得た。
なお、表1に記載のタッキファイヤーは以下に示すとおりである。
D-125:ロジン系タッキファイヤー(荒川化学社製、商品名:ペンセルD-125、軟化点:120~130℃)
T145:テルペンフェノール樹脂(ヤスハラケミカル社製、商品名:YSポリスターT145、軟化点:140~150℃)
A-75:ロジン系タッキファイヤー(荒川化学社製、商品名:スーパーエステルA-75、軟化点:70~80℃)
〔ゲル分率〕
実施例等で得られた粘着剤層約0.1gをサンプリング瓶に採取し、酢酸エチル30mLを加えて4時間振盪した後、このサンプル瓶の内容物を200メッシュのステンレス製金網で濾過し、金網上の残留物を100℃で2時間乾燥して乾燥質量を測定した。次式により、粘着剤層のゲル分率を求めた。
ゲル分率(質量%)=(乾燥質量/粘着剤層採取質量)×100(%)
23℃、50%RH条件下で、実施例等で得られた両面粘着シートの一方の紙セパレーターを剥がし、露出した粘着剤層面に厚み25μmのポリエチレンテレフタレートフィルムを裏打ちした。その後、もう一方の紙セパレーターを剥がし、露出した粘着面をポリプロピレン板に2kgのローラーを用いて圧着した。貼付面積は20mm幅×50mmとした。貼付から20分後に、110℃かつ乾燥条件で20分間保温し、その後100gの荷重を粘着剤層面に対して90°方向に鉛直にかけ、60分後のはがれ長さ(mm)を測定した。測定時間内に試験片がポリプロピレン板から落下した場合は、落下までに要した時間を測定した。落下した場合は「落下」と記載した。
Claims (6)
- (メタ)アクリルポリマー(A)が、カルボキシル基含有モノマーを含む重合性二重結合含有モノマーの可逆的付加開裂連鎖移動(RAFT)重合体である請求項1に記載の粘着剤用組成物。
- (メタ)アクリルポリマー(A)が、水酸基およびアミノ基から選ばれる少なくとも1種を有するモノマーの使用量が0.3質量%以下である重合性二重結合含有モノマーの重合体である、請求項1または2に記載の粘着剤用組成物。
- 請求項1~4のいずれか1項に記載の粘着剤用組成物から得られる粘着剤層。
- 請求項5に記載の粘着剤層を有する粘着シート。
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